The present invention is directed to monomeric and polymeric compositions based upon urethane surfactants which are generally derived from linear, branched, or aromatic compounds of synthetic or natural origin, preferably from tertiary amines and diisocyanate compounds. The urethane betaines of the present invention may be incorporated into personal care formulations such as cosmetics, dental care products and toiletries to improve or modify at least two of the characteristics of such formulations.
Surfactants, such as Betaines, amine oxides and quaternaries (from C6-C22) have been used on a commercial basis in the cosmetic, toiletry and personal care industry for the past 40 years primarily as surfactants for their mildness and lack of irritation on a commercial basis. The aforementioned surfactants have been prepared from natural oils, such as coconut oil, palm kernal oil, soybean oil, safflower seed oil, corn oil, etc. The oils are reacted with amine derivatives such as dimethylaminopropylamine, diethylaminopropyl amine, etc. via transamidation with caustic catalysts to yield the linear C6 through C22 dimethylaminopropyl amine derivatives. Similarly, linear fatty acids ranging from C6 through C22 have been reacted to form the linear tertiary amine salts which upon application of heat drove off water to form the corresponding C6 through C22 linear dimethylaminopropylamine derivative. Aromatic acids such as benzoic acid as well as branched acids similarly have been reacted to form the resultant aromatic dimethylamidopropyl amine or iso-dimethylamido propylamine which could serve as a building block for the betaine. However, aromatic backboned surfactants have not found wide commercial use.
Over the years, betaines, amine oxides and quaternaries have become commodity products used in a wide array of applications ranging from shampoos, nonirritating baby shampoos, liquid soaps, dish detergents (to preclude introduction of phosphate builders), body scrubs, shaving creams, etc. When the pH of a cosmetic or toiletry product incorporating betaines is dropped to a pH slightly below about 7.0, the betaine becomes mildly cationic and improved feel and combability of hair results. When coupled with amine oxides, the combination yields a high degree of hair detangling characteristics in shampoos.
The inclusion of betaines and amine oxides into liquid soaps in combination with alpha olefin sulfonates and amides ranging in size from C12-C18 at a pH under 7.0, effectively functions as a thickening agent in a liquid soap which leaves the hands soft and silky. Betaines with a preponderance of C12 through C14 groups have been shown to be effective foaming agents when used in combination with sodium lauryl sulfate, sodium lauryl ether sulfates and alpha olefin sulfonates.
Betaines as well as amine oxides with chain lengths ranging from C16 through C22 exhibit special effectiveness as thickening and conditioning agents. The introduction of a betaine of dimethyl oleyl betaine into a shampoo or body lotion does little to promote foam; however, viscosity of a resultant formulation with up to 2.0 percent of higher molecular weight chains such as oleyl, erucyl, arachidyl give significant thickening.
Betaines, amine oxides and quaternaries have been found to be extremely effective as tartar-removing agents in toothpaste formulations. A great deal of work had been done in this research arena in the early ""70s. When betaines were introduced into toothpaste formulations, teeth were found to be xe2x80x9csqueaky cleanxe2x80x9d. However, a major drawback in using these compositions was the taste which was very difficult to mask with flavors. Consequently, as a result of this foul taste, no major brands of toothpaste were introduced to the marketplace. Numerous betaine derivatives were made but were never commercialized.
Betaines have also demonstrated properties of corrosion inhibition and have been incorporated into industrial formulations. The lower molecular weight betaines ranging from C6 through C18 have found wide use in industrial applications.
Another area in which betaines and amine oxides have been used in large volume with considerable success is in the oil and oil-field-related industry. As surfactants in the oil industry, betaines and amine oxides are used as emulsifiers, wetting agents, antifoulants, cleaners and detergents. With respect to paraffinic chemicals, betaines are used as surfactants for breaking up emulsions and as defoamers, for cleaning tanks, dispersing paraffins and as wetting agents for paraffinics. Betaines are also used in aqueous-isopropanol solutions to improve water injectivity in water flooding, as corrosion preventatives in floods, as a surfactant for clarification in water containing H2S, to assist in the control of fouling due to microbial action, to enhance scale inhibition and also as an emulsifier and coupler in oil well formulations.
With the fairly recent concern with nitrosoamines which may be present as minor contaminants in widely used diethanolamide amines (derived from fatty acids as well as methyl esters), betaines and amine oxides have become used in extremely large quantities in consumer products such as shampoos, body baths, liquid soaps, etc.
It is an object of the present invention to provide novel betaine, amine oxide and quaternary compositions which can be used to improve or modify the characteristics of personal care products. Methods for improving or modifying the personal care products are another object of the present invention.
Secondary objects of the invention, depending upon the specific embodiment, may include one or more of the following:
A. To provide urethane polymers for use as conditioners, antistats, detanglers, facilitators for ease of wet/dry combing, to assist in the minimization of split ends (in hair products), as emulsifiers and for the maximization of color in colored hair products (dyes).
B. To introduce into hair and skin contacting formulations polymeric urethane surfactants that will maintain stability and become mildly cationic when used at a pH of less than about 7.0.
C. To increase the xe2x80x9cadhesionxe2x80x9d of the entire molecule to the hair and skin through the structure of the urethane linkages.
D. To provide a basis for xe2x80x9cthickeningxe2x80x9d or increasing viscosity in given hair and skin contacting formulations as a result of the polymeric urethane structure of the surfactant molecule used.
E. To provide polymeric urethane surfactants for use as a cosmetic raw material in skin and hair contacting formulations to yield mildness and at the same time have low LD50 values.
F. To introduce novel and unique polymeric betaines, amine oxides and quaternaries that are derived from, but not necessarily limited to, renewable vegetable sources making it possible to avoid bovine derived raw materials.
These and other objects of the present invention may be readily gleaned from the description of the invention which follows.
The present invention relates to polymeric urethane compounds, preferably derived from components obtained from naturally occurring sources.
The present invention relates to compounds of the formula: 
where Rxe2x80x2 is a C2 through C36 (preferably, C6 through C22) linear, cyclic or branch-chained saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, monomeric or dimeric, an aromatic group, including a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzyl group; Rxe2x80x3 is selected from a C1 through C36 (preferably, C6 through C22) linear, branch-chained or cyclic saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, monomeric or dimeric, a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl, substituted alkylphenyl or alkylbenzyl group, an alkylene oxide group (R4xe2x80x94O)m where R4 is a C2 to C8 alkylene group, preferably a C2 to C6 alkylene group, preferably a C2 to C4 unbranched alkylene group, more preferably a C2 to C3 alkylene or a mixture of C2 and C3 alkylene groups (preferably as polyethylene-co-polypropylene oxide blocks) and m is 2 to 150; 
Rxe2x80x2xe2x80x3 is selected from a C1 through C36 (preferably, C6 through C22) linear or branch-chained, cyclic, saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, monomeric or dimeric or an aromatic group, including a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl, substituted alkylphenyl or alkylbenzyl group; and
R1 is selected from a C1 through C36, preferably a C2 through C22 linear or branch-chained saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, an aromatic group, including a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl, substituted alkylphenyl or alkylbenzyl group;
R2 is a free electron pair (i.e., R2 is not substituted, especially where Rxe2x80x3 is a 
group),
O (to form N-oxide), a hydrogen or a quaternium group, or a mixture of hydrogen and quaternium groups, with the proviso that when R2 is H and/or a quaternium group, the nitrogen to which said hydrogen or quaternium group is bonded is positively charged and forms a salt with a negatively charged counterion T;
R3 is selected from a C1 through C36, preferably a C2 through C22, more preferably a C10 to C22 linear or branch-chained saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, an aromatic group including a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzyl group or an alkylene oxide group (R4xe2x80x94O)m where R4 is a C2 to C8 hydrocarbon (alkylene) group, preferably a C2 to C6 hydrocarbon (alkylene) group, preferably a C2 to C4 unbranched hydrocarbon (alkylene) group, more preferably a C2 to C3 or a mixture of C2 and C3 (preferably as polyethylene-co-polypropylene oxide blocks) and m is an integer from 2 to 150;
each of X and Y is independently selected from a C1 through C36, preferably C1 through C22, even more preferably C1 through C10 linear, cyclic or branch-chained saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, an aromatic group including a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzyl group;
n is an integer from 1 to 1000, preferably 2 to about 150, even more preferably about 2 to 20, even more preferably about 2-10; and even more preferably about 2 to 4;
W is H, a sulfosuccinate group or a C4-C10 alkyl sulfonate group,
a phosphate group 
group where V is a C1 through C10 linear, cyclic or branch-chained saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzyl group and R5 is a C1 to C6 alkyl group or a metal cation selected from the groups consisting of Na+, K+, Ca++ and Mg++ (preferably Na+ or K+).
In the compositions described above, R1 is preferably an unsubstituted saturated or unsaturated branched or unbranched alkyl group, R2 is preferably O to form an N-oxide with the adjacent nitrogen atom or a hydrogen or quaternium group, Rxe2x80x3 is preferably a 
group or a 
group;
X is preferably a C1 to C4 hydrocarbon group and Y is preferably a C6 to C22 linear or branch-chained saturated or unsaturated hydrocarbon which is even more preferably obtained from a naturally occurring fatty acid most preferably obtained from a plant source which contains a pendant hydroxyl group;
Rxe2x80x2xe2x80x3 is preferably a C6 to C22 linear or branch-chained saturated or unsaturated hydrocarbon which is even more preferably obtained from a narturally occurring fatty acid most preferably obtained from a plant source which contains a pendant hydroxyl group;
Rxe2x80x2 is preferably a saturated hydrocarbon containing pendant methyl groups, for example a substituted cyclohexyl group such as an isophorone group and W is most preferably H or a sulfosuccinate group or a related group containing an unsaturated double bond and optionally, an acid moiety (such as maleic acid which can be used to form a sulfosuccinate group) which may be modified to contain a sulfonate group.
In the present compositions, the quaternium group R2 is a carbon containing group (generally, in order to form a quaternium group the nitrogen bonds to a carbon within the quaternium group) preferably selected from C1 to C10 alkyl groups, more preferably methyl and ethyl groups, benzyl and alkyl benzyl groups, among numerous others including substituted and unsubstituted saturated and unsaturated hydrocarbon groups including acetate groups (from chloroacetic acid), a propylene glycol group (from epichlorohydrin), ether groups and related groups, among numerous others.
Although the counterion T group may be any group which is anionic and is compatible with the chemistry of the present invention, when R2 is H (the nitrogen to which the H is bonded forms a tertiary ammonium group), preferred T counterion groups include, for example, carboxylates (derived from carboxylic and polycarboxylic acids, preferably dicarboxylic acids, most preferably dicarboxylic acids such as dilinoleic acid, among others), anionic chloride, bromide and iodide, sulfates (mono-, di- and tri-anionic sulfate, preferably tri-anionic sulfate) and phosphates (mono-, di- and tri-anionic, preferably tri-anionic phosphate), among numerous others, with carboxylates and dicarboxylates being particularly preferred.
In the case where R2 is a quaternium group as described generally hereinabove, counterion T is preferably anionic chloride, bromide, iodide, fluoride, sulfate (preferably mono- or di-anionic, preferably alkyl substituted mono-anion such as methyl or ethyl sulfate, more preferably ethyl sulfate, especially where R3 is an ethyl group) anionic chloride and sulfate (alkyl substituted mono-anionic sulfate) being the preferred counterion T. Monoanionic T groups may be represented by Txe2x88x92, and dianionic T groups are represented by Txe2x95x90.
Compositions which are representative of ammonium salts or quaternium salts (i.e., where R2 is H or a quaternium group) according to the present invention described above may be further represented by the structure: 
Where each of R1, R2, R3, Rxe2x80x2, Rxe2x80x3, Rxe2x80x2xe2x80x3, T, V, W, X, Y and n is the same as described above.
Preferred embodiments of ammonium where T is derived from a dicarboxylic acid such as dilinoleic acid and which provide two carboxylate groups or moieties per molecule T, may be represented by the structure: 
Where T is a dimer dilinoleate dianion.
Preferably, each of R1, R2, Rxe2x80x3 and Rxe2x80x2xe2x80x3 are linear or branched-chain saturated or unsaturated alkyl or alkylene groups which are derived or obtained from fatty acids or fatty amines of natural original, most preferably, fatty amines obtained from plant sources. Preferred hydroxyl containing acids for use in the present invention include ricinleic acid and dimethylolpropionic acid (which allows one to produce a dihydroxyl-substituted fatty amide fatty nd/or fatty amines for use in the present invention include, for example, soyamine,
Substituents (xe2x80x9csubstitutedxe2x80x9d) which may be used in the present compositions may include for example, halogens such as fluorine, chlorine and bromine, nitro groups, amine groups, substituted amine groups, hydroxyl groups, alkoxy groups, unsubstituted and substituted alkoxy groups, alkyl groups or substituted alkyl groups, among numerous others. Preferably, the substitutents in the present compositions are limited to halogen groups, most preferably fluorine and chlorine. One of ordinary skill in the art will be able to recognize modifications which readily may be made to the present compositions to instill desirable characteristics in the present compositions and to avoid undesirable reactions during polymerization such as chain termination, crosslinking and other reactions which may occur with reactive substituents such as hydroxyl groups and amines or amine-containing groups.
The groups R1 and R3 are preferably derived from such hydroxyl containing natural oils such as castor oil, or from tertiary amines containing alkoxide or alkylene oxide groups, the alkoxide groups preferably being linear and having chain lengths ranging from C6 through C22, and the alkylene oxide groups (R4xe2x80x94O)m, where R4 is a C2 to C8 alkylene group and m ranges from 2 to 150 wherein a terminal hydroxyl group would be consumed in the reaction with diisocyanate to product a urethane. The tertiary amines could then be reacted to form betaines, amine oxides or salts, with the salts ranging in chain length from C6 through C50 carbon atoms.
The present invention also relates to compounds of the structure: 
Where Rxe2x80x3xe2x80x3 is a 
R6 is is selected from a C1 through C36, preferably a C2 through C22, even more preferably a C2 to C10 linear or branch-chained saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, an aromatic group including a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzyl group or an alkylene oxide group (R4xe2x80x94O)m where R4 is a C2 to C8 hydrocarbon (alkylene) group, preferably a C2 to C6 hydrocarbon (alkylene) group, preferably a C2 to C4 unbranched hydrocarbon (alkylene) group, more preferably a C2 to C3 or a mixture of C2 and C3 (preferably as polyethylene-co-polypropylene oxide blocks) and m is an integer from 2 to 150;
Z is H or a C1 through C10 linear, cyclic or branch-chained saturated or unsaturated hydrocarbon group which is substituted or unsubstituted, a phenyl or benzyl group or substituted phenyl or benzyl group, an alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzyl group;
and each of R1, R2, R3, Rxe2x80x2, Rxe2x80x3, Rxe2x80x2xe2x80x3, T, V, X, Y and n is the same as described above.
Compounds of the present invention where R2 is H and T is a dianionic species such as dilinoleic acid are clearly contemplated here.
Compounds according to the present invention exhibit primary utility as surfactants, wetting agents, anti-irritants, conditioners, viscosity builders in shampoos and liquid hand soaps. In addition, they assist in mending split ends of hair, have low levels of skin, eye and ingestion toxicity and can be used to disperse hair dyes and promote the hair dye function.
By selecting the diisocyanate, using the appropriate chain length, taking the degree of unsaturation in the backbone and by adjusting the degree of alkoxylation judicious use of either ethylene or propylene oxide), it is possible to introduce water solubility/insolubility or emulsification characteristics to the polymer.
By building a polymeric surfactant based on urethane technology, it is possible to offer a product that has substantivity to both the skin and hair based on the urethane bonds. Furthermore, adhesion and substantivity of the molecule may be enhanced by the cationic structure of the composition which, in certain embodiments which employs an amine which is converted to the ammonium salt, becomes more cationic with decreasing pH. Additionally, these polymeric urethanes are compatible with a wide array of surfactants that are commonly used in the cosmetic and toiletry industry such as amides, amine oxides, sulfosuccinates, sulfonates, sulfated castor oil, etc., since they share similar backbones.
Other properties and characteristics of the compounds of the present invention which make them highly desirable to the cosmetic and toiletry industry are as follows:
A. Extremely low order of toxicity and irritation
B. Low color
C. Low odor
D. Excellent compatibility in cosmetic formulations
E. Solubility with amides, sulfonates sulfosuccinates, and sulfobetaines
F. Nonrancidification
G. Coupling characteristics
H. Solubility in water, glycols and lower molecular weight alcohols
I. Ability to be synthesized to become insoluble in water, glycols and lower molecular alcohols (propoxylated versions)
The following definitions shall be used throughout the specification in describing the present invention.
The term xe2x80x9cpersonal care productxe2x80x9d is used throughout the specification to describe a cosmetic or toiletry product which is preferably used on or in contact with the hair, skin and/or nails and which include effective concentrations of one or more of the compositions according to the present invention. Personal care products include, for example, cosmetics, floating bath oils, after shaves, creams, lotions, deodorants, including stick deodorants, pre-electric shave lotions, after-shave lotions, antiperspirants, shampoos, conditioners and rinses and related products, among others, including skin care products, eye makeups, body shampoos, protective skin formulations, lipsticks, lip glosses, after-bath splashes, presun and sun products, including sunscreens. Virtually any chemical product which comes into contact with the hair or skin and which may include effective amounts or concentrations of one or more of the compositions according to the present invention may be considered a personal care product according to the present invention.
The term xe2x80x9csurfactantxe2x80x9d is used throughout the specification to describe compounds according to the present invention which contain a tertiary amine group which has been further reacted to form or otherwise forms an N-oxide group, a quaternary amine group or a carboxylate salt. Certain compounds according to the present invention are also referred to as urethane betaines, urethane N-oxides or urethane quaternary compounds because of the existence of at least one betaine group, N-oxide group or quaternary group (preferably more than two) and at least one urethane group (preferably, at least two).
The term xe2x80x9chydrocarbonxe2x80x9d is used throughout the specification to describe various substituent groups according to the present invention. The term hydrocarbon embraces, but is not limited to, for example, alkyl, alkene groups (including those groups containg more than one unsaturated double bond), alkyne groups, aryl groups, aralkyl groups and related groups which are comprised of carbon and hydrogen atoms, such as alkylene groups (which are similar to alkyl groups except they are substituted at two carbons of the hydrocarbon with atoms or substituents other than hydrogen rather than one as is the case with alkyl groups) and related hydrocarbon radicals which may be found in the present compositions. In certain cases the terms xe2x80x9calkylxe2x80x9d (or related alkyl groups such as methyl, phenyl, benzyl, etc.) is used interchangeably with a di-substituted hydrocarbon group such as an alkylene, methylene, phenylene, etc. Hydrocarbons according to the present invention may be linear, cyclic or branch-chained, substituted (i.e., have pendant halogen, hydroxyl or other groups) or unsubstituted (i.e., comprised exclusively of C and H atoms) monomeric or dimeric (or even of higher order), aromatic, including phenyl or benzyl or substituted phenyl or benzyl group, alkylphenyl, alkylbenzyl or substituted alkylphenyl or alkylbenzy, etc.
The term xe2x80x9chydroxyl terminatedxe2x80x9d refers to an end group on the compositions according to the present invention which contains a free hydroxyl group at its terminal end. Although hydroxyl terminated groups are primarily and preferably primary hydroxyl groups, the terminal hydroxyl group may be found in a position such that the hydroxyl group is also a secondary or even a tertiary hydroxyl group. Hydroxyl terminated groups in compositions according to the present invention may be further reacted with carboxylic acids to form esters or isocyanates to form urethane groups as more fully described herein.
The term xe2x80x9ctertiary aminexe2x80x9d is used to describe an amine to which is attached at least three carbon-containing groups, each of the groups being covalently bonded to the amine group through a carbon atom within the group.
The terms xe2x80x9chydroxyl containing amidoalkyl dialkyl aminexe2x80x9d or dialkoxyamine are used throughout the specification to delineate a linear, aromatic or branched chain hydrocarbon containing at least one hydroxyl group in the backbone or two hydroxyl groups as part of the dialkoxy functionality in the terminus of the molecule and may include such tertiary amidoamine compounds as diethoxyethylamine, diethoxypropylamine, dipropoxyethylamine, dipropoxypropylamine, bis-polyoxyethylene ranging from 2 to 100 units of ethylene oxide and bis-polypropoxyamine ranging from 2 to 100 units of propylene oxide.
The compounds may be unsubstituted or substituted (generally, halogen or hydroxyl substituted), but preferably only hydroxyl substituted. The linear backbone of the present invention may be totally saturated or contain exclusively single bonds (fully saturated) or at least one double or triple bond (unsaturated) which affect the solubility and viscosity of the final product.
The chain length of the present invention may range from 6 carbon atoms to 36 carbon atoms in the backbone with the preferred chain being in the range of 10 to 22 carbon atoms. The moles of alkoxylation may range from 2 to 150 moles that may be condensed on to the chain length ranging from 6 to 36 carbon atoms.
Furthermore, it is possible to vary the ethylene oxide propylene oxide ratios from 1 to 99 percent ethylene propylene oxide and conversely to vary the ratio of 99 to 1 of the ethylene propylene oxide which will affect properties of solubility, viscosity and emulsification properties.
The term xe2x80x9cdiisocyanatexe2x80x9d is used throughout the specification to describe a linear, cyclic or branch-chained hydrocarbon having two free isocyanate groups. The term xe2x80x9cdiisocyanatexe2x80x9d also includes halogen substituted linear, cyclic or branch-chained hydrocarbons having two free isocyanate groups. Exemplary diisocyanates include, for example, isophoronediisocyanate, m-phenylene-diisocyanate, p-phenylenediisocyanate, 4,4-butyl-m-phenylene-diisocyanate, 4-methoxy-m-phenylenediisocyanate, 4-phenoxy-m-phenylenediisocyanate, 4-chloro-m-phenyldiisocyanate, toluenediisocyanate, m-xylylenediisocyanate, p-xylylenediisocyanate, 1,4-napthalenediisocyanate, cumene-1,4-diisocyanate, durene-diisocyanate, 1,5-napthylenediisocyanate, 1,8-napthylenediisocyanate, 1,5-tetrahydronapthylenediisocyanate, 2,6-napthylenediisocyanate, 1,5-tetrahydronapthylenediisocyanate; p,p-diphylenediisocyanate; 2,4-diphenylhexane-1,6-diisocyanate; methylenediisocyanate; ethylenediisocyanate; trimethylenediisocyanate, tetramethylenediisocyanate, pentamethylenediisocyanate, hexamethylenediisocyanate, nonamethylenediisocyanate, decamethylene-diisocyanate, 3-chloro-trimethylenediisocyanate and 2,3-dimethyltetramethylenediisocyanate, among numerous others. Isophorone diisocyanate is used the preferred diisocyanate used in the present invention.
The term xe2x80x9ccarboxylic acidxe2x80x9d as used herein describes organic acids which may contain one or more carboxylic acid moieties preferably ranging in size from C2 to C50 or more. The term xe2x80x9cmonocarboxylic acidxe2x80x9d is used to describe organic acids which contain only one carboxylic acid moiety. The term xe2x80x9cpolycarboxylic acidxe2x80x9d is used to describe organic acids which contain at least two carboxylic acid moieties. Those polycarboxylic acids which contain only two carboxylic acid moieties may also be referred to in this specification as xe2x80x9cdicarboxylic acidsxe2x80x9d.
Exemplary carboxylic acids for use in the present invention include, for example, pentanoic acid, neopentanoic acid, caproic acid, caprylic acid, capric acid, heptanoic acid, neoheptanoic acid, octanoic acid, iso-octanoic acid, 2-etlhylhexanoic acid, nonanoic acid, isononanooic acid, decanoic acid, iso-decanoic acid, neodecanoic acid, undenanoic acid, undecylenic acid, lauric acid, isolauric acid, myristic acid, palmitic acid, stearic acid, hydroxy stearic acid, isostearic acid, arachidonic acid, tallow fatty acid, arachidic acid, behenic acid, lignoceric acid, lauroleic acid, myristoleic acid, palmitoleic acid, olelic acid, gadoleic acid, erusic acid, ricinoleic acid, linolenic acid, linoleic acid, lactic acid, glycolic acid, mandelic acid, eicosopentaoic acid, phenylstearic acid, retinoic acid, salicylic acid and benzoic acid, among numerous others, including dimer acids, trimer acids, adipic acid, azealeic acid, malic acid, succinic acid, dodecandioic acid, citric acid, tartaric acid, sebacic acid, fumaric acid, glucaric acid, glutaric acid and oxalic acid, among others.
Preferred polycarboxylic acids for use in the present invention include, for example, C2-C50 dicarboxylic acids, including dimer, trimer and tetramer acids which are made from the dimerization, trimerization or tetramerization of long-chain unsaturated acids, such as linoleic acid, among numerous other acids, including mixtures of these acids, more preferably including C5-C37 dicarboxylic acids and mixtures of these acids. Dilinoleic acid is a preferred dicarboxylic acid. Other acids which may be preferably used in the present invention include, for example, adipic acid, azealeic acid, malic acid, succinic acid, dodecandioic acid, citric acid, tartaric acid, sebacic acid, fumaric acid, glucaric acid, glutaric acid and oxalic acid, among others. Preferred dicarboxylic acids containg carboxylic groups at the terminal ends of the molecule.
Other exemplary polycarboxylic acids include, for example, polymeric products containing carboxylic (carboxylate) side chains, such as acrylic or (meth)acrylic, polyesters, cellulosic polymers, polyvinyl alcohol, polysiloxanes, oligo and polypeptides, among numerous others.
Carboxylic acids may be used in the present invention to neutralize tertiary amines to function as counter ion (T) in the ammonium salt which is formed during neutralization of the free amine groups. Alternatively, carboxylic acids, especially fatty acids obtained from natural sources, may be used advantageously to prepare the tertiary amines or amidoamines which may be used to prepare compositions according to the present invention.
The term xe2x80x9cquaternizing agentxe2x80x9d is used throughout the specification to describe compounds which are used to react with tertiary amines to produce quarternary salts according to the present invention. Quaternary salts are salts which are produced when a tertiary amine is reacted with a quaternizing agent to produce a quaternary amine (quaternium) which is substituted with four carbon-containing groups. The quaternary amine produced is cationic and is generally found complexed with an anionic group or xe2x80x9ccounterionxe2x80x9d, which is generally derived from the quaternizing agent used to produce the quaternary amine. Exemplary quaternizing agents for use in the present invention include, for example, dimethyl sulfate, diethyl sulfate, methyl bromide, benzyl chloride, ethyl benzyl chloride, methyl benzyl chloride, dichloroethyl ether, epichlorohydrin, ethylene chlorohydrin, methyl chloride, pyridinium chloride and allyl chloride, among others, such that the group reactive with the amine produces an Nxe2x80x94R3 group with the amine and the positively charged quaternary amine group is complexed with an anionic group or counterion, which is represented as Txe2x80x94. The counterion may be any group which is anionic and is compatible with the chemistry of the present invention and preferably is an anionic chloride, bromide, iodide, fluoride, carboxylate (from, for example the use of chloroacetic acid or sodium monochloroacetate as the quaternizing agent to provide an acetate which can provide both a quaternium group as well as the counterion) sulfate (mono- or di-anion, preferably alkyl substituted mono-anion such as methyl or ethyl sulfate, more preferably ethyl sulfate) and phosphate (mono-, di- and tri-anion, preferably tri-anion), among numerous others, with anionic chloride and sulfate (alkyl substituted mono-anion) being the preferred counterion T.
The term xe2x80x9calkylene oxidexe2x80x9d refers to a polymeric group of repeating units of the general formula (R7xe2x80x94O)nxe2x80x94 where R7 is a C2 to C8 alkyl group, preferably a C2 to C6 alkyl group, preferably a C2 to C4 unbranched alkyl group, more preferably a C2 to C3 or a mixture of C2 and C3 (preferably as polyethylene-co-polypropylene oxide blocks) unbranched alkyl groups and n ranges from 2 to 150 units (corresponding to 2 to 150 moles of alkylene oxide) within that group. Most preferably, R7 is C2 (ethylene oxide).
The term xe2x80x9csurfactantxe2x80x9d is used throughout the present invention to describe compounds which reduce surface tension, condition, emolliate, prevent flyaway hair, function as antistats, emulsify, solubilize hair dyes (colors), assist in the reduction of split (hair) ends, are of a low order of toxicity, assist in detangling hair, give excellent wet/dry hair properties, function as anti-irritants, viscosity builders, and because of the urethane functionality, increase adhesion to the hair shaft; as well as soften and emolliate the skin. It is an unexpected result that the present compositions may be varied to accommodate numerous physicochemical characteristics in a single composition.
The term xe2x80x9cemolliatexe2x80x9d or xe2x80x9cemollientxe2x80x9d is used throughout the specification to describe concentrations of amounts of compound of the present invention which are included in the personal care products to provide emolliency to skin contacting formulations such as body shampoos, liquid soaps, body conditioners, toners and effective emollient properties for treating epithelial tissue. Such amounts may range from as little as 0.05% to 15% by weight or more of the personal care products according to the present invention.
The term xe2x80x9ceffective amountxe2x80x9d is used throughout the specification to describe concentrations or amounts of compounds according to the present invention which are effective in conveying desired characteristics such as conditioning, adhesion, softening, prevention of static electricity buildup, the promotion of wet and dry hair combability, detangling of hair, solubilization and compatibility with other surfactants, promotion of viscosity, reduction of toxicity, promotion of color solubilization, minimization of split hair ends, etc. to a formulation in the cosmetic, toiletry or personal care industry.
Compounds as outlined in the present invention may be prepared by synthetic methods known in the art. Generally speaking, a general procedure involves the reaction of a monofunctional or difunctional hydroxy fatty amine (for example, ricinoleylamide containing glycerine or bis-alkoxy amino or polyalkoxyamino or polyhydroxy functional product) based on a linear, iso or aromatic chain, with a diisocyanate in the presence of heat and either an amine or tin catalyst such as stannous octanoate. Each isocyanate moiety is thereby converted to a urethane moiety while maintaining the presence of xe2x80x9cfree and unreactedxe2x80x9d tertiary amines. These xe2x80x9cfreexe2x80x9d tertiary amines may then quaternized, i.e., reacted with, with for example, sodium monochloracetate, chloracetic acid in the presence of sodium of potassium hydroxide to form the resulting betaine. The free tertiary amines described above may also be reacted with other quaternizing agents as otherwise described herein to produce quaternary amines surfactants. Alternatively, the tertiary amine may simply be reacted with a carboxylic acid to form a tertiary ammonium salt with a carboxylate counterion. In addition, the xe2x80x9cfreexe2x80x9d tertiary amines may be reacted with hydrogen peroxide or another oxidizing agent to form amine oxides which can be used in the cosmetic, toiletry and personal care industry in skin and hair contacting formulations.
By way of example, an amido amine containing at least one free hydroxyl group (preferably at least two hydroxyl groups) may be prepared from castor oil or any related hydroxyacid. The free hydoxyl groups may then be reacted with a diisocyanate to produce a oligomeric or polymeric urethane composition which contains a tertiary amine group. The tertiary amine group may then be quaternized, acidified (with a carboxylic acid or a related acid to produce a sulfate, phosphate or chloride salt) or oxidized to produce the corresonding quaternary amine salt, ammonium salt or N-oxide containing composition. Alternatively, alkoxylated fatty amines such as soyamine, oleylamine and cocamine or related alkoxzylated fatty amines which contain at least two hydroxyl groups, among others, may be prepared and then reacted with diisocyanates to produce an oligo or (poly)urethane composition, which may be further reacted to produce the quaternary amine salt, ammonium salt or N-oxide containing composition.
The terminal hydroxyl groups in any of the above compsitions may be esterified or otherwise end-capped with carboxylic acids such as maleic acid and related unsaturated acids to produce an unsaturated ester group (preferably having 1,4-enone which is activated to form a sulfonate) which can be further derivatized to an alkyl sulfonate ester or salt with sodium bisulfite or a related sulfonating agent. Preferably, these alkyl sulfonates are C4-C10 alkyl sulfonate groups. Alternatively, the compositions may be end-capped with a phosphate group or other group which is anionic.
Compounds as outlined in the present invention may be used as conditioners for keratinous and epithelil tissue such as hair, nails and skin. By the introduction of conditioners and hair softening amounts of the polymeric urethane betaines, it is possible to introduce effective personal care, toiletry and cosmetic products that will achieve highly desirable characteristics.
Effective amounts of the surfactants of polymeric urethanes of the present invention may also function as coupling and clarifying agents in formulations in the personal care, toiletry and cosmetic industry, where glycols with their inherent viscosity reduction properties have been used in the past. In numerous instances, the novel betaine urethane polymers have effectively replaced ethoxylated sorbitan monoesters of lauric and/or oleic acids for their clarification, coupling and solubilization properties. Additionally, the products of the present invention are naturally derived, are biodegradable and are compatible with biological systems and demonstrate a low order of toxicity and irritation.
The present compounds inherently bestow upon a cosmetic formulator the ability to achieve a wide range of desirable end characteristics that may be sought in a given formulation by selecting polymeric urethanes according to the present invention and adding it to a composition to be improved or modified. Indeed, it is an unexpected result of the present invention that personal care products may have at least two characteristics, and often, more than two characteristics of the formulation substantially modified by the introduction of a single composition. For example, with the increase in the degree of ethoxylation of an ethoxylated tertiary amine, it is possible to achieve increased water solubility and increased viscosity. By selecting a backbone with increased unsaturation, it is possible not only to increase water solubility but also to decrease viscosity of the polymeric urethane betaine. The higher the degree of unsaturation present in the molecule, the greater the effectiveness of softening, conditioning., prevention of flyaway hair and increased benefits of wet and dry combing, etc. As one increases both the number of urethane groups within the composition, the molecular weight of the composition will increase as will the viscosity (generally) and ability of the compsoition to adhere to keratinous tissue. Those of ordinary skill engaging in routine experimentation will be able to determine the preferential chain lengths for optimum results. Beneficial characteristics for foaming are to be found in the C12 through C18 chain lengths. Chain lengths primarily ranging from C18 through the C22 area will tend to have a greater effect upon viscosity of a given formulation.
Compositions according to the present invention may be used to formulate skin and hair contacting formulations in the cosmetic, toiletry and personal care industries that have excellent aesthetics heretofore unachievable.
It has also been unexpectedly discovered that the polymeric urethanes of the present invention derived from hydroxyl containing long chain isomeric or aromatic tertiary amines when reacted to form surfactants such as betaines or amine oxides or reacted with long chain fatty acids ranging in chain length from C6 through C36 or dimerized with dimer or trimer acids that the properties achievable from an aesthetic viewpoint far surpass those properties that alone can be ascribed to the polymeric urethanes of hydroxyl containing long chain, isomeric or aromatic tertiary amines themselves. In essence, the surfactants derived from hydroxyl containing long chain linear, isomeric or aromatic tertiary amines far surpass the properties of emulsification, detangling, conditioner, softening, prevention of flyaway hair, antistatic characteristics, facilitation of wet and dry hair combing, repair of split ends (hair). Further, the surfactants so derived also assist in hair colorization and are of a low order of dermal and ocular toxicity. The combination of characteristicds which can be instilled in a personal care product using a single composition according to the present invention without relying on numerous additives is unexpected. That all of these characteristics could be instilled with a substantial absence of toxicity is particularly unexpected.
It has been further surprisingly discovered that the polymers of the present invention are excellent hair conditioners and show effectiveness in the following systems:
Shave creams
Women""s toiletries for shaving preparations
Depilatories
Relaxers
Conditioners
2-in-1 shampoos
Furthermore, the present invention provides the following personal care formulations:
Unexpectedly and dramatically reduces split ends in conditioning and shampoo formulations;
Provides good wet/dry combing;
Provides body and shine to hair;
Reduces tangles and provides a more manageable base for styling;
Softens coarse hairs to provide easier shaving;
Provides a closer, less damaged shave.
In general, compositions according to the present invention are included in personal care products/formulations in effective amounts, i.e., amounts which produce an intended effect. The amount of composition generally ranges from about 0.05% to about 15% by weight or more of personal care formulations according to the present invention. In preferred embodiments of emulsion-based foromulations, compositions according to the present invention are included in amounts ranging from about 0.1% to about 5% by weight. In the case of shampoos and conditioners, compositions according to the present invention are included in amounts ranging from about 0.1% to about 3% by weight of the formulation.
For example, in shampoos, rinses, conditioners, hair straighteners, hair colorants and permanent wave formulations, the compositions according to the present invention preferably comprise about 0.1% to about 20% by weight, more preferably about 0.25% to about 3% by weight of the final end-use hair-care composition. Other components which may be included in hair-care formulations include, for example, a solvent or diluent such as water and/or alcohol, other surfactants, thickeners, coloring agents, preservatives, additional conditioning agents and humectants, among numerous others.
In the case of shave creams and gels, after-shave lotions and shave-conditioning compositions (for example, pre-electric shave formulations), the compositions according to the present invention are included in amounts ranging from about 0.25% to about 15% or more by weight, more preferably about 0.5% to about 10% by weight. Other components which may be included in these end-use compositions include, for example, water, and at least one or more of emollients, humectants and emulsifiers and optionally, other conditioning agents, medicaments, fragrances and preservatives.
In the case of skin lotions and creams, the present compositions are included in amounts ranging from about 0.25% to about 15% by weight, more preferably, about 0.5 to about 10% by weight. Additional components which may be employed in these compositions include, for example, water, emollients and emulsifers and optionally, other conditioning agents medicaments, fragrances and preservatives.
In the case of sunscreens and skin-protective compositions, the present compositions are included in amounts ranging from about 0.25% to about 15% or more by weight, preferablyt about 0.5% to about 7.5% by weight of the final formulations. Additional components which may be employed in these compositions may include, for example, a UV absorbing composition such as para-amino benzoic acid (PABA) or a related UV absorber or a pigment such as TiO2, water or oil, and optional components including, for example, one or more of an oil, water, suspending agents, other conditioning agents and emollients, among others.
In the case of bar and liquid soaps, compositions according to the present invention are included in amounts ranging from about 0.25% to about 20% by weight or more, preferably about 0.5% to about 10% by weight. Additional components which may be included in bar and liquid soaps include water and surfactants and optionally, bacteriacides, fragrances and colorants, among others.
When the present invention was tested in a shave cream as compared to commercially available products, it was reported that 24 of our of 25 participants preferred the shave cream incorporating the present invention, with only one participant being undecided for the following:
Closeness of shave
Less Damage
Softer skin feel
Longer lasting fragrance
Smoother shave
Ease of shave
It was surprisingly discovered that when the present invention was introduced into 2:1 conditioning shampoos and into hair conditioners, results indicated that the present invention yielded excellent conditioning of damaged hair; and, in fact, performed better than commercially available products on the marketplace. A panel composed of 35 individuals selected formulations at close to 90% over products that are commercially available. Furthermore, the present invention when incorporated into both shampoos and conditioners, the following unforeseen effects were observed:
Better xe2x80x9cfeelxe2x80x9d
Better appearance
Increased viscosities
Also, emulsion formulations performed better than normal allowing the formulator to reduce the maximum temperature of the phases, thereby decreasing manufacturing time and, in effect, reducing costs.
The following examples of compounds (and their proposed INCI names) according to the present invention have been prepared:
The reaction product of dimethylaminopropyl ricinoleamide with isophorone diisocyanate (IPDI) and sodium monochloracetate FOAMTAINE PPI-RC;
INCI Name: Recinoleamidopropyl Dimethyl Glycine/IPDI Copolymer
The reaction product of bis-polyoxyethylene (15) soyamine with IPDI and sodium monochloracetate.FOAMTAINE PPI-SA-15
INCI Name: PEG-15 Soyamine Bis Hydroxethyl Glycine/IPDI Copolymer
The reaction product of bis-polyoxyethylene (15) amine with IPDI and sodium monochloracetate FOAMTAINE PPI-CA-15
INCI Name: PEG-15 Cocamine Bishydroxyethyl Glycine/IPDI Copolymer
The reaction product of bis-polyoxyethylene (15) tallow amine with IPDI and sodium monochloracetate FOAMTAINE PPI-TA
INCI Name: PEG-2 Tallowamine Bishydroxyethyl Glycine/IPDI Copolymer
The reaction product of bis-hydroxyethyl(2) Soyamine/IPDI Copolymer with Hydrogen Peroxide FOAMOX PPI-SA
INCI Name: N-Soyamine N,N-Bishydroxyethyleamine Oxide/IPDI Copolymer
The reaction product of bis-hydroxylethyl (2) Soyamine IPDI Copolymer and Diethyl sulfate FOAMQUAT PPI-SA
INCI Name: N-Soyamine N,N-Hydroxyethyl N-Ethyl Ammonium Ethyl Sulfate/IPDI Copolymer
The reaction product of bis-Hydroxyethyl (15) Soyamine/IPDI Copolymer and Diethyl sulfate FOAMQUAT PPI-CA-15
INCI Name: PEG-15 Cocamine-N-Ethyl Ammonium Ethyl Sulfate/IPDI Copolymer
The reaction product of bis-Hydroxyethyl (2) Soyamine/IPDI Copolymer and Dimer Dilinoleic acid POLYDERM PPI-SA-D
INCI Name: PEG-2Soyamine/IPDI Copolymer Dimer Dilinoleate
The reaction product of bis-Hydroxyethyl (2) Soyamine and IPDI POLYDERM PPI-SA
INCI Name: Di-PEG-2 Soyamine/IPDI Copolymer
The reaction product of Polyoxyethylene (15) Cocamine and IPDI POLYDERM PPI-CA-15
INCI Name: PEG-15 Cocamine/IPDI Copolymer
The reaction product of Recinoleamidopropyl Dimethyamine and Glycerine with IPDI POLYDERM PPI-RC
INCI Name:Ricinoleamidopropyl DimethylAmine-Glyceryl/IPDI Copolymer
The reaction product of Ricinoleyamidopropyl Dimethyamine and Glycerine with IPDI POLYDERM PPI-RCD
INCI Name: Recinoleamidopropyl DiumethylAmine-Glyceryl/IPDI Copolymer Dimer Dilinoleate
Structural formulas of the above-described surfactants and other surfactants according to the present invention are presented herein. 
The present invention is now described, purely by way of illustration, in the following examples. It will be understood by one of ordinary skill in the art that these examples are in no way limiting and that variations of detail can be made without departing from the spirit and scope of the present invention.